Alkoxy substituted carbanilates

ABSTRACT

IN WHICH X is oxygen or sulfur, R and R1 are independently lower alkyl, R and R1 taken together are ethylene or trimethylene, R2 is alkyl, monocyclohexylamino, monoalkylamino, monoalkenylamino, dialkylamino, alkoxy, alkylthio, haloalkyl, substituted-phenyl wherein said substituents are methyl, monochloro or dichloro. The compounds are useful as herbicides.   Meta-phenoxy acetals having the formula

United States Patent [191 Teach [451 Apr. 29, 1975 1 ALKOXY SUBSTITUTEDCARBANILATES [75] Inventor: Eugene G. Teach, El Cerrito, Calif.

[73] Assignee: Stauifer Chemical Company, New

York, NY.

[22] Filed: Aug. 3, 1973 [2]] Appl. No.: 385,515

Related U.S. Application Data [62] Division of Ser. No. 124,541, March15, 1971, Pat.

Primary Examiner-Lorraine A. Weinberger Assistant Examiner-L. A. ThaxtonAttorney, Agent, or Firm-Harry A. Pacini; Daniel C. Block; Edwin H.Baker [57] ABSTRACT Meta-phenoxy acetals having the formula in which Xis oxygen or sulfur, R and R are independently lower alkyl, R and Rtaken together are ethylene or trimethylene, R is alkyl,monocyclohexylamino, monoalkylamino, monoalkenylamino, dialkylamino,alkoxy, alkylthio, haloalkyl, substitutedphenyl wherein saidsubstituents are methyl, monochloro or dichloro. The compounds areuseful as herbicides.

3 Claims, N0 Drawings ALKOXY SUBSTITUTED CARBANILATES This is a divisionof application Ser. No. 124,541 filed Mar. 15, 1971, now US. Pat. No.3,780,104.

This invention relates to certain novel amide and urea substitutedmeta-phenoxy acetals which are useful as herbicides. The compounds ofthe present invention are new compositions of matter and correspond tothe general formula OR O-CH CH in which X is oxygen or sulfur, R and R,are independe'ntly lower alkyl, R and R taken together are ethylene ortrimethylene, R is alkyl, monocyclohexylamino, monoalkylamino,monoalkenylamino, dialkylamino, alkoxy, alkylthio, haloalkyl,substituted-phenyl wherein said substituents are methyl, monochloro ordichloro.

In the above description, the following preferred embodiments areintended for the various substituent groups: for R and R lower alkylpreferably includes, unless otherwise provided for, those members whichcontain from 1 to 4 carbon atoms, inclusive, in both straight chain andbranched chain configurations, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, sec.-butyl and isobutyl; for R alkyl preferablyincludes those members which contain from 1 to 8 carbon atoms instraight and branched chain configurations, for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec.- butyl, amyl, isoamyl, n-hexyl,isohexyl, 2,4,4- trimethylpentyl, l,l-dimethylbutyl, l-methylbutyl; theterms alkoxy and alkylthio, preferably includes those members of thegroups which contain from 1 to 6 carbon atoms, such as methoxy, ethoxy,propoxy, hexoxy, methylthio, ethylthio, propylthio and hexylthio andtheir isomers in branch chained configurations. The term haloalkylpreferably includes those members of the group which contain 1 to 4carbon atoms, inclusive, and mono, di, tri, tetra, and penta halogens,either the same or mixed of the group fluorine, chlorine and bromine.Preferably, fluorine and chlorine, such as monochloromethyl,dichloromethyl, trichloromethyl, monofiuoromethyl, difluoromethyl,trifluoromethyl, chloro fluoromethyl, dichlorofluoromethyl,difluorochloromethyl, chlorobromomethyl, dibromomethyl, monochloroethyl,1 1 -dichloroethyl, 1,2-

chlorofluoroethyl, 1,2-difluoroethyl, pentafluoroethyl,tetrachloromonofluoroethyl, l-monochloropropyl, 1,2- dichloro-l,2-difluoropropy1, monochlorobutyl, monofluorobutyl, and monobromobutyland the like. The terms monoalkylamino and dialkylamino, preferablydenote the groups and -N respectively, in which R R and R independentlyare alkyl groups which contain 1 to 6 carbon atoms, inclusive, in eitherstraight chain or branched chain configurations, for example, methyl,ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, amyl, isoamyl, n-hexyland isohexyl. The term monoalkenylamino, preferably includes thosemembers which contain 2 to 4 carbon atoms, inclusive, that is, whereinthe alkenyl substituent contains at least one double bond and contains 2to 4 carbon atoms, inclusive, such as vinyl, alkyl, propenyl-l,butenyl-l, butenyl-2 and the like.

The compounds of this invention have been found to be active herbicidesof a general type. That is, certain members of the class have been foundto be herbicidally effective against a wide range of plant species. Amethod of controlling undesirable vegetation of the present inventioncomprises applying an herbicidally effective amount of theabove-described compounds to the area or plant locus where control isdesired.

An herbicide is used herein to mean a compound which controlsor modifiesthe growth of plants. By a growth controlling amount is meant an amountof compound which causes a modifying effect upon the growth of plants.Such modifying effects include all deviations from natural development,for example, killing, retardation, defoliation, desiccation, regulation,stunting, tillering, stimulation, dwarfing and the like. By plants it ismeant germinant seeds, emerging seedlings, and established vegetation,including the roots and above-ground portions.

The compounds of the present invention are prepared by several differentmethods, depending upon the nature of the starting materials and theproducts desired. For example, two preferred routes to obtain theinstant compounds are as follows. The acetaldehyde acetal group isintroduced into meta-aminophenol to yield a meta-amino acetalintermediate. This intermediate is further reacted with a suitable acidchloride,

'chloroformate or isocyanate to yield the desired substituted anilide,carbanilate or urea phenoxy acetal, according to scheme 1.

I QM,

0R BrCH CH OR OR O-CH CH OCH CH 2 OR 2 OR NH NEE-R in which X, R, R andR have the meanings given hereinabove.

The reactions proceed readily in the liquid phase. The employment of asolvent is also useful, facilitatingprocessing, as well as agitation ofthe reactants. Solvents such as acetone are conveniently employed. Thereactions are carried out at temperatures that permit operation in theliquid phase. The temperatures are between about room temperature andreflux temperature of the solvent, if a solvent is employed. In eachinstance, after the reaction is complete, the recovery of the product iscarried out by normal work-up procedures such as crystallization,sublimation or distillation.

The compounds of the present invention and their preparation are moreparticularly illustrated by the following examples. Following theexamples is a table of compounds which are prepared according to theprocedures described herein.

EXAMPLE I Preparation of Intermediate: m-aminophenoxyacetaldehydediethylacetal.

m-Aminophenol, 109 g., is dissolved in 500 ml. of dimethyl formamide and216 g. of 25% sodium methoxide in methanol is added and the excessmethanol stripped off under vacuum. Bromoacetaldehyde diethylacetal, 200g., is added and the mixture heated at reflux for 5 hours and thenpoured into water. The product is taken up in methylene chloride, washedwith dilute base and water, dried over anhydrous magnesium sulfate andthe solvent stripped under vacuum. The yield of the title compound is130 g., n 1.5151.

The dimethyl acetal is prepared similarly from chloroacetaldehydedimethylacetal.

EXAMPLE 11 Preparation of m-propionamidophenoxyacetaldehydediethylacetal.

Nine and nine-tenths grams of 3-hydroxy propionanilide is dissolved in100 ml. of dimethylformamide, 13 g. of 25% sodium methoxide in methanolis added. This is followed by 11.8 g. of bromoacetaldehyde diethylacetaland the mixture is heated at reflux for' 8 hours, stirred for anadditional 16 hours and then poured into water. The product is taken upin methylene chloride, washed with dilute base and acid, dried overmagnesium sulfate and the solvent removed under vacuum. The yield of thetitle compound is 9 g., n 1.5160.

EXAMPLE n1 Preparation of m-methylureidophenoxyacetaldehydedimethylacetal.

Thirteen and eight-tenths grams of m-aminophenoxyacetaldehydedimethylacetal is dissolved in ml. of acetone, 4.5 g. ofmethylisocyanate is added and the mixture heated at reflux for an hour.The solvent is stripped under vacuum. There is obtained 17.4 g. of thetitle compound, u 1.5388.

EXAMPLE 1V Preparation of m-propionamidophenoxyacetaldehydedimethylacetal.

Thirteen and eight-tenths grams of m-aminophenoxyacetaldehydedimethylacetal is dissolved in 100 g. of acetone and 7.5 g.of triethylamine and 6.6 g. of propionylchloride is added portionwisewith cooling and stirring. The mixture is poured into water, the producttaken up in methylene chloride, dried over magnesium sulfate and thesolvent stripped under vacuum. The yield of the title compound is 15.9g., n 1.5220.

EXAMPLE V Preparation of m-S-methylthiocarbamylphenoxyacetaldehydediethylacetal.

Eleven and three-tenths grams of m-aminophenoxyacetaldehydediethylacetal is dissolved in 100 ml. of acetone and 6.5 g.of triethylamine. The mixture is cooled in a water bath and 6.7 g. ofmethyl chlorothioformate is added portionwise. After addition iscomplete, the mixture is poured into approximately 500 ml. of water andthe product taken up with methylene chloride, dried over magnesiumsulfate and the solvent removed under vacuum. The yield of the titlecompound is 12 g., n 1.5355.

The following is a table of the illustrative compounds which areprepared according to the aforementioned procedures. Compound numbershave been assigned to them and are used for identification throughoutthe balance of the specification.

TA BLE I OR 0-CH CH COM- mp. C. POUND NUMBER X R R R or m,

1 0 CH c 14 C l-1 1.5 2 0 cm, c n, i-C;,H, 1.5047 3 0 CH c 11 tC,1-l1.4970 4 0 cm 0 H, C -,H,C1-1(CH 1.4950 5 O C H C 11 C H C(C1-l 1.4938 6O C H C H CHaNH- 1.5215 7 O C H C H (CH N 1.5184 8 O C 11 C 11 C H NH1.5179 9 O C 11 C H nC ,H NH 1.5066 10 S C H 5 C 11 CH -,NH 1.5367 11 OC H C 11 CH;,O 1.5083 12 O C l-1 C H CH -,S- 1.5355 13 0 CH CH C H1.5220 14 O CH CH C -,H CH(CH;,) 1.5098 15 0 CH CH CH;,NH 1.5388 16 O CHCH (CH3) N 1.5320 17 0 CH CH nC.,H NH- 1.5270

I-IERBICIDAL SCREENING TESTS As previously mentioned, theherein-described compounds produced in the above-described manner arephytotoxic compounds which are useful and valuable in controllingvarious plant species. Compounds of this invention are tested asherbicides in the following manner.

Pre-emergence herbicide test.

On the day preceding treatment, seeds of seven different weed speciesare planted in individual rows using one species per row across thewidth of the flat. The seeds used are hairy crabgrass (Digitarissanguinalis (L.) Scop.), yellow foxtail (Setaria glauca (I...) Beauv.watergrass (Echinochloa crusgalli (L.) Beauv.), California red oat(Avena sativa (L.)), redroot pigweed (Amaranthus retroflexus (L.)),Indian mustard (Brassica juncea (L.) Coss.) and curly dock (Rumexcrispus (L.)). Ample seeds are planted to give about to 50 seedlings perrow, after emergence, depending on the size of the plants. The flats arewatered after planting. The spraying solution is prepared by dissolving50 mg. of

the test compound in 3 ml. of a solvent, such as acetone, containing l%Tween 20 (polyoxyethylene sorbitan monolaurate). The following day eachflat is sprayed at the rate of 20 pounds of the candidate compound per80 gallons of solution per acre. An atomizer is used to spray thesolution onto thesoil surface. The flats are placed in a greenhouse at80F. and watered regularly. Two weeks later the degree of weed controlis determined by comparing the amount of germination and growth of eachweed in the treated flats with weeds in several untreated control flats.The rating system is as follows:

0 no significant injury (approximately 0-10 per cent control) 3 slightinjury (approximately 10-40 per cent control) 6 moderate injury(approximately 40-70 per cent control) 9 severe injury or death(approximately -100 per cent control) An activity index is used torepresent the total activity on all seven weed species. The activityindex is the sum of the numbers divided by 3, so that an activity indexof 21 represents complete control of all seven weeds. The results ofthis test are reported in Table II.

Post-emergence herbicide test.

Seeds of five weed species, including hairy crabgrass, watergrass,California red oats, Indian mustard, and curly dock and one crop, pintobeans (Phaseolus vulgaris), are planted in flats as described above forpreemergence screening. The flats are placed in the greenhouse at 7285F.and watered daily with a sprinkler. About 10 to 14 days after planting,when the primary leaves of the bean plant are almost fully expanded andthe first trifoliate leaves are just starting to form, the plants aresprayed. The spray is prepared by weighing out 50 mg. of the testcompound, dissolving it in 5 ml. of acetone containing 1% Tween 20(polyoxyethylene sorbitan monolaurate) and then adding 5 ml. of water.The solution is sprayed on the foliage using an atomizer. The sprayconcentration is 0.5% and the rate would be approximately 20 lb/acre ifall of the spray were retained on the plant and the soil, but some sprayis lost, so it is estimated that the application rate is approximately12.5 lb/acre.

Beans are used to detect defoliants and plant growth regulators. Thebeans are trimmed to two or three plants per flat by cutting off theexcess weaker plants several days before treatment. The treated plantsare placed back in the greenhouse and care is taken to avoid sprinklingthe treated foliage with water for 3 days after treatment. Water isapplied to the soil by means of a slow stream from a watering hose,taking care not to wet the foliage.

Injury rates are recorded 14 days after treatment.

The rating system is the same as described above for- .the pre-emergencetest where (0), (3), (6), and (9) are used for the different rates ofinjury and control. The injury symptoms are also recorded. The maximumactivity index for complete control of all the species in thepost-emergence screening test is 18. This index repre-' sents the sum ofthe rating numbers obtained with the six plant species used in the testdivided by 3. The herbicide activity index is shown in Table II.

TABLE II HERBICIDAL ACTIVITY SCREENING RESULTS HERBICIDAL ACTIVITY INDEXCOMPOUND Pre-emergencc Post-emergence NUMBER (20 lb/A) (12.5 lb/A) l l8l7 2 l8 l7 3 l3 l5 4 I7 l8 5 l4 l8 6 l8 l8 7 l9 l8 8 l7 l7 9 18 l8 l 613 ll l0 l7 l2 l7 17 I3 l9 l7 l4 l9 l8 I 21 I8 16 l7 l8 l7 l9 l8 l8 l2l5 l9 l9 I8 20 7 II 21 9 I5 22 l4 I5 23 l6 I8 24 7 I4 25 l0 16 26 6 I527 9 I8 28 9 I5 29 4 I4 30 0 4 3l 0 7 32 3 ll 33 5 ll 34 0 II 35 0 6 36I 8 21 70-10071 control of all seven plant species tested pre-emergencc.I8 70-l00% control of all six plant species tested post-emergence.

The compounds of the present invention are used as pre-emergence orpost-emergence herbicides and are applied in a variety of ways atvarious concentrations. In practice, the compounds are formulated withan inert carrier, utilizing methods well-known to those skilled in theart, thereby making them suitable for application as ducts, sprays, ordrenches and the like, in the form and manner required. The mixtures canbe dispersed in water with the aid of a wetting agent or they can beemployed in organic liquid compositions, oil and water, water in oilemulsions, with or without the addition of wetting, dispersing oremulsifying agents. An herbicidally effective amount depends upon thenature of the seeds or plants to be controlled and the rate ofapplication varies from 1 to approximately 50 pounds per acre.

The phytotoxic compositions of this invention employing an herbicidallyeffective amount of the compounds described herein are applied to theplants in the conventional manner. Thus, the dust and liquidcompositions can be applied to the plant by the use of powerdusters,boom and hand sprayers and spray-dusters. The compositions can also beapplied from airplanes as a dust or a spray because they are effectivein very low dosages. In order to modify or control growth of germinatingseeds or emerging seedlings, as a typical example, the dust and liquidcompositions are applied to the soil according to conventional methodsand are distributed in the soil to a depth of at least one-half inchbelow the soil surface. It is not necessary that the phytotoxiccompositions be admixed with the soil particles,

since these compositions can be applied merely by spraying or sprinklingthe surface of the soil. The phytotoxic compositions of this inventioncan also be applied by addition to irrigation water supplied to thefield to be treated. This method of application permits the penetrationof the compositions into the soil as the water is absorbed therein. Dustcompositions, granular compositions or liquid formulations applied tothe surface of the soil can be distributed below the surface of the soilby conventional means such as discing, dragging or mixing operations.

The phytotoxic compositions of this invention can also contain otheradditaments, for example, fertilizers, pesticides and the like, used asadjuvant or in combination with any of the above-described adjuvants.Other phytotoxic compounds useful in combination with theabove-described compounds include, for example 2,4-dichlorophenoxyaceticacids, 2,4,5-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyaceticacid and the salts, esters and amides thereof; triazine derivatives,such as 2,4-bis(3-methoxypropylamino)-6- methylthio-S-triazine;2-chloro-4-ethylamino-6-isopropylamino-S-triazine, and 2-ethylamino-4-isopropylamino-6-methylmercapto-S-triazine, urea derivatives, such as3-(3,4-dichlorophenyl)-l,l-dimethyl urea and3-(p-chlorophenyl)-l,l-dimethyl urea and acetamides such asN,N-diallyl-a-chloroacetamide, and the like; benzoic' acids such as3-amino-2,5- dichlorobenzoic; and thiocarbamates, such as S-propyldipropylthiocarbamate; S-ethyl-dipropylthiocarbamate,S-ethyl-cyclohexyl-ethyl-thiocarbamate, S-ethylhexahydro-ll-l-azepine-l-carbothioate and the like. Fertilizers usefulin combination with the active ingredients include, for example,ammonium nitrate, urea and superphosphate. Other useful additamentsinclude materials in which plant organisms take root and grow, such ascompost, manure, humus, sand and the like.

The concentration of a compound of the present invention, constitutingan effective amount in the best mode of administration in the utilitydisclosed, is readily determinable by those skilled in the art.

Various changes and modifications are possible without departing fromthe spirit and scopeof the invention described herein and will beapparent to those skilled in the art to which it pertains. It isaccordingly intended that the present invention shall only be limited bythe scope of the claims.

What is claimed is:

1. A compound having the formula O-CH CH NHC-R in which R and R areindependently lower alkyl and R is alkoxy.

2. A compound according to claim 1 in which R and R are each ethyl and Ris methoxy.

3. A compound according to claim 1 in which R and R, are each methyl andR is methoxy.

1. A COMPOUND HAVING THE FORMULA
 2. A compound according to claim 1 inwhich R and R1 are each ethyl and R2 is methoxy.
 3. A compound accordingto claim 1 in which R and R1 are each methyl and R2 is methoxy.